Certain water-soluble high molal oxyalkylated esters, and method of making same



' Patented Mar. 13, 1945 i I-TE STATES oERTAiN WATER-SOLUBLE. menOXYALKYLATED ESTERS, .AND' .METHOD OF MAKING SAME Melvin De Groote,"University City, and Bernhard 'Keiser, WebsterGroves, Mm, assignors toPetrolite Corporation, 'Ltdi, Wilmington, Del, a

corporation of Delaware No Drawing. Original applicationlulyfi, 1941,Serial No. 401,377. Divided and this applica-- tion March 9,1943,-Serial l\ l'o;478,588'

'12 Claims. ((11. 2 66-404) fli'his invention relates to a newchornical'prodnot, our present application'being a division of ourpending application for patent Serial No; 401,377, filed July 7, 1941,for Process for breaking petroleum emulsions, which subsequently maturedas U. S. Patent No. 2,324,489, dated July.2'0, 19 13.

One object of our invention is'to provide a new chemical product orcompound thatis 'particu-' 1 larlyadapted for use as a demulsifier inthe reso lution of crude oil emulsions. j

Another object of ourinvention is -to provide a practicable method formanufacturing said new chemical product or compound.

.Althollgh one of the primary objects of our invention is to provide anew compound or comester. of the kindpreviously described. Theforposition of matter that is an eflicientjdemulsifier for crude oilemulsions of the watef-in-oil type,

the said compound or composition of matter may be employed in otherarts, as hereinafter indicated.

The new chemical compound or composition of'matter' herein described, isexemplified by the mation'of the compound may beindicated' by! thefollomngreaction, although obviously, it is immaterial 'what fparticularprocedure is employed to produce the-particular chemical compound or.

acidic, or preferably, neutral ester, derived by complete esteriflcationof one mole of a poly; alkylene glycol of the kind hereinafterdescribed, with two moles of a fractional ester derived from ahydroxylated material of the kind herein described, and a polybasiccarboxy 'acidhaving not '1 over six carbonatoms. If a hydroxylate'dmaterial, indicated for the sake of convenience, by the formulaT.OH-,&in which. T is'anlalcohol residue, is reacted with a polybasiccarboxy acid,l which, similarly, may conveniently be of the dibasic typeand indicated by the formula HOOC.D.COOH, in which D is a. dicarboxyacidresidue, then the fractional ester obtained by reaction betweenequimolar quantii ties may be indicated by'the following formula:noocpnoom llhepolyethylene glycol may be characterizedby materials ofthe kind such as heptaethylene glycol, -octaethylene glycol,nonaethyleneglycol, deca'ethylen'e glycol, to and includingheptadecaethylene glycol. For convenience, these poly ethylene glycolsmaybe indicated by the follow ing;formula r in which-m varies from 7through 17. v

Instead of polyethylene glyc'ols, one may use polypropylene glycols or.polybutylene glycols.

Thus, for convenience, in the broadest aspect, the

' more desirableto use an indicated previously, thegpolybasic acidsemployed arelimitedtothe type having not more than six carbon atoms, forexample, oxalic, nialonic, succinic, I glutaric, and adipic. Similarly,one' 'm'ay employ acids such 'as furnaric, maleic,

glutaconic, and various others, including citric,

malic', tartaric, and the like. The selection of the particular tribasicor dibasic acid employed is usually concerned largely with convenienceof manufacture of the finished ester, and also of the price-of thereactants. Generally speaking, the

Y higherthe-temperature employed, the easier it is to obtain-largeyields of the esterified product. Although oxalic acid is comparatively.cheap, it decomposessomewhat readily at slightly above the boilingpoint ofwa'ter. For this-reason, it is acid'which is-morejresistant'to'pyrolysis,"Similarly,when a polybasic acid is available in theform'ofgan anhydride,

' sum anhydride is apt to produce the ester with greaterease-than theacid-itself. For this reason, maleic anhydrideis particularlyadaptable;and also,everything'else considered, the cost is comparativelylow-on a.per'molar basis, even though somewhat higher on a-per pound basis.fSuc'cinic w acid or the anhydride has manyof the'attr'active qualitiesof 'maleic an'l ydride'; and "this is also true of adipic acid.Florpurposes of brevitmthe bulk of the compounds hereinafterillust'ratedrefer to the use of maleictanhydride, although it is understood that anyother suitable .polybasic acid may be employed. Furthermore, forpurposes of convenience, reference is made to the use of polyethyleneglycols. As has been previously indicated, such glycols can be replacedby suitable polypropylene or polybutylene compounds.

As far as the-range of oxyalkylated compounds employed as reactants isconcerned, it is our preference to employ those having approximately8-12 oxyalkylene groups, particularly 8-12 oxyethylene' 7 groups.

resent the upper range of distillable glycols; and

they may be conveniently referred to as upper distillable ethyleneglycols. There is no particularly goodprocedure for making a sharperseparation on a commercial scale {and it is understood that mixtures ofone or moreof the glycols may.

be employed, as well as a single glycol. As pointed out, it isparticularly preferred to employ no'naethylene glycol as commerciallyavailable, although it is understood that this product contains otherhomologs, as indicated.

Substantially as desirable as the upper distillable polyethyleneglycols, are the lower non-distillable polyethylene glycols. ,Thesematerials are available in the form of a waxy water-solubl'e material,and the general range may vary somewhat from decato tetradecaethyleneglycol. As is well understood, the method of producing such glycolswould cause 'some'higher'homologs to be formedf and thus, even in thisinstance, there may be present some'oxyethyle'ne -glycols within thehigher range above indicated. One need not point out that-these.particular compounds consist of mixtures, and that in some instances,particularly desirable esters are obtained by making mixtures of theliquid nonaethylene glycol with the soft, waxy, lower non-distillablepolyethylene glycols. For thesake of convenience, reference intheexampleswill be tonon- 'aeth'ylene glycol; and calculations will bebased o'nia theoretical molecular weight of 414. Actually, inmanufacture, the molecular weight of the glycol employed, whether ahigher distillable polyethylene glycol or a lower nondistillablepolyethylene glycol, or a mixture of the same, should be determinedandreaction conducted on the basis of such determination, particularly inconjunction with the hydroxyl oracetyl value, ,1 'It has been previouslypointed out that it is immaterial how the compounds herein contemplatedare manufactured, although we have found it most desirable to react theselected glycol, or mixtures of glycols, with maleic anhydride in aratioof two'moles of the anhydride for one mole bf "the glycol. 'Undersuch circumstances, we

have found'little tendency to form longer chain polymers; and in fact,the product of reaction, if conducted at reasonably low temperatures,appears to'be largely monomeric. For convenience, such intermediateproductmay then be considered as a dibasic or polybasic acid. One moleof the intermediate sotobtained is then reacted with twomoles of thealcoholic material of the kind subsequently described,

' 'j'Itis to-be noted, however, that if one prepares a" fractionalacidic ester, then if two moles of the fractional acidic'ester arereacted with one mole of the polyethylene glycol, there is no ossibilityfor the formation of polymeric types of esterification products underordinary conditions.

The hydroxylated compounds employed as reactants in one mode ofmanufacture of the present compounds are hydroxylated acylated monoaminobodies free from'ether linkages, and of the following formula:

in which R.COO represents the oxy-acyl radical derived from a monobasicdetergent-forming acid; R2 represents a hydrogen atom or a nonhydroxyhydrocarbon radical, or the acylated radical obtained by replacing ahydrogen atom of the hydroxyl group of an alkylol radical by the acylradical of a monobasic carboxy acid having less than eight carbon atoms;11 represents a small Whole number which is less than 10; m 1

represents the numeral 1, 2, or 3; 111. represents the numeral 0, 1, or2; and. m" represents the numeral 0, 1, or 2, with the proviso thatm+m'+m"=3 One can obtain or manufacture chemical compounds whosecomposition is indicated by the following formulas:

no 6 ojozni If, in the above formulas, R2 represents an amino hydrogenatom, as well as a substituent therefor, then the formulas abovedescribed may be summarized by the following formula:

However, the radical Cal-I4, which appears in the above formula, mayrepresent anysimilar radical, such as a CzHe radical, a C4Ha radical,etc., and therefore, the above formula may be indicated as follows:

taooooinmn.

' In the above formulas it has been pointed out cal; or R2 may representthe acylated radical obtained by replacing a'hydrogen atom of thehydroxyl group of an alkylolradical, or the equivalent thereof, by theacyl radical of a monobasic carboxy acid, such as acetic acid, butyricacid, heptoic acid, or the like; all of which are Char acterized byhaving less than eight carbon atoms. The alkylol radical, prior toacylation, niaybe a hydroxy ali'cycli'c or a hydroxyaralkyl radical,provided the hydroxy radical is attached to the aliphatic residue of thearalkyl radical. j,

In the above formula, as has been pointed out, RG represents theoxy-acyl or acid radical derived from the acid R.C0O;H. 'acoonre resentsany monobasic detergent-forming carboxy acid, such as a typical fattyacid or abietic acid or n'aphthenic acid.

Typical fatty acids are those which occur .in' naturally-occurring oilsand fats, and, generally have eight or more carbon atoms and not over 32carbon. atoms. acid, stearic acid, linoleic acid, linolenic acid,ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. Theseacids combine. with alkali to produce soap or soap-like materials, andare com- Cornmon examples include oleic "If thetriethanolamine, employedin the above formula, is replaced byzethyl diethanolamine, then onewouldobtain one of'theremaining types of tertiary amines illustrated.Reference is made to, Patent No. 2,167,349, dated July 25,1939, to-

De Groote, .Keis erv and Blair.

In. the remainin'gtype of material there is an amino hydrogen atompresent. The manufacture of such material may be illustrated bythefollow OOH enamel-#1 110000211401 00 0110111401 R.-COO.C2H4C1 0.010110111401 noooolnloi 11.000.0211 01 N113 R.COO-C2H4.NH2

aoooclm B.COO.C2H4NHH 0- 0 /NH OHC2H4 R.COO.C:H4

/NH I y I v 0110,11. However, if maximum yields are. not necessary, oneneed not resort to reactions of the kind previously described to producesecondary amines,

monly referred to as being monobasic detergentforming carboxy acids. V aThe alkylol radical, previously. referred to,

priorto esterification, maybe a hydroxy alicyclic or a hydroxy aralkylradical, provided the hybut one may employ the following type ofreaction: v 1

OH.C2H4

aooo-om 011.com

11.00 "NH a aoooognlh droxy radical is attached to the aliphatic resiv edue of the aralkyl radical. 03mg YNH+CH(OHV)' to the amines abovedescribed, which hap- 011.0111. OELG'zH; I pen to be tertiary amines, itmay bewell to point NH out that these may be formed readily by areaction involving an ester of the selected deter- R 000 OEOZHgent-forming acid, for instance,.a fatty acid ester, '1 OH-CHENEY v a'snch as the glyceride, and a corresponding amine. Q" gg gggfig,aRooo'camNfl-zfogmmmf This may be illustrated-1n the followmgmanner:R110 I I OHLCZHA OH-G2H4-N (I) R.OOO\ 011C211;

RUOQ-CzHb 0H.C2H4 3000mm R000 Onea -N v a omcime 0111x 11):

OH.CzH|

OH.O:H4

OH.G2H4

OH.C2H4N 11.0 o o OH O H R.COO-O:H5 OHOIH RCoo 0H. 2 4\ R.GOO.C2H4 .0H-N H (H) RI-C00 0 2 4 R C CgHl ,N ZCBHKO .1 H.0 H 3000-03116 OH OH aooo1 OH.C2H4 N 0H.C'2H4 *(II'D'ILCO'O 011mm a'ooocim OH/CzH'r -N:R.CO0.C:H4 CaHK fi itooo circle. 1 .nlo'oocolm Suitable primary andsecondary amines, which may be employed to produce materials of the kindabove described, include the following: Diethanolamine,monoethanolamine, ethyl ethanolamine, methyl ethanolamine,propanolamine, dipropanolamine, propyl propanolamine, etc. Otherexamples include cyclohexylolamine, dicyclohexylolamine, cyclohexylethanolamine, cyclohexyl propanolamine, benzylethanolamine,benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine,octadecylethanolamine, cyclohexanolethanolamine, etc. Y

Similarly, suitable tertiary amines which may be employed include thefollowing: triethanolamine, diethanolalkyla-mines, such as diethanolethylamine, diethanol propylamine, etc. Other examples include diethanolmethylamine, tripropanolamine, dipropanol methylamine, cyclohexanoldiethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine,'dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyldiethanolbenzyl dipropanolamine, tripentanolamine, trihexanolamine,hexyl ethanolamine, octadecyl diethanolamine, etc.

Reference is again made to the formula which summarizes the varioushydroxylated amines used a intermediate raw materials, viz;

aooocflmn).

I r (T) (011cm) m in which the characteristics have their previoussignificance. Attention is directed to the fact that where thesubstituted alkyl radical OH:R.COO.CH-

appears, a suitable non-aryl radical other than an aliphatic residue mayserve as the functional equivalent; for instance, an alicyclic radicalderived from a cyclohexyl radical, or an aralkyl radical derived from abenzyl radical. In other words, in the hereto appended claims referencesto the CnHiln radical, as such, or as an alkyl radical or residue, isintended in the broad sense to include the alicyclic radical or residue,or the aralkyl radicals or residues which are the equiva lent thereof.There is no intention to include an aromatic radical where there is adirect linkage between the aromatic nucleu and the amino nitrogen atom,for the reason that such products have little or no basicity and do nothave the characteristic properties of the amines previously described.

In indicating the various hydroxylated tertiary amines of the non-aryltype, which may be employed to produce the amine contemplated as thedemulsifying agent of the present process, it is desirable to indicatethat amines of the type where a hydroxy acyl radical replace a hydrogenatom of the hydroxyl radical of the hydroxy tertiary amine, are notincluded within the broad class of hydroxy tertiary amines, unless thereis another hydroxyl radical attached to the usual alkyl radical. Forinstance, if ethyl diethanolamine is treated with two moles of lacticacid so as to form the dilacetyl compound of the following formula:

CzHs

then it is understood that such materials would not represent a hydroxytertiary amine within the meaning or scope, as herein employed. If, onthe other hand, triethanolamine were treated with lactic acid, so as togive monolactyl triethanolamine of the following composition:

' on o cmono-o-cnm OHCgHr-N OHCzH4 then such compound would be included,due to the presence of one or more hydroxyl radicals attached to thealkyl radicals.

Similarly, in indicating the various hydroxylated primary or secondaryamines of the non-aryl type, which may be employed to produce the aminecontemplated as the demulsifying agent of the present process, it isdesirable to indicate that amines of the type where a hydroxy acylradical replaces a hydrogen atom of the hydroxyl radical of a hydroxyprimary or secondary amine, are not included within the broad clas ofhydroxy tertiary amines, unless there is another hydroxyl radicalattached to the usual alkyl radical. For instance, if ethanolamine istreated with lactic acid so as to form the lactyl derivative of thefollowing formula:

selected detergent-forming acid, or ester, as, for

example, a fatty oil and the selected hydroxy tertiary amine, are mixedin suitable proportions and heated at some point above the boiling pointof water, for instance, 110 0., and at a point below the decompositionpoint of the amine or the fatty oil, for instance, 180 0., for asuitable Period of time, such as two to eight hours. Mild agitation isemployed. A catalyst, such as sodium oleate, sodium carbonate, causticsoda, etc., may be present in amounts of about one-half of 1% or less.It is noted that the fatty acids are employed in this instance, in theform of an ester, to wit,

- the glyceride, although, as previously pointed out,

- ucts derived by esterification, rather than amidification. lAnysuitable ester may be employed,

but it is often most convenient to employ the glyceride of a fatty acid,for instance, t-riricinolein. The selected glyceride and the selectedhydroxy secondary amine are mixed in suitable proportions and heated atsome point above the boiling point of water, for instance, 0., and belowthe decomposition point of the amine or fatty material, for instance,0., for a suitable period amounts of about-one-half percent, or less; Itis to be noted that the fatty acids arepre'sent in ester form and not inthe form of the free acid, and thus there is no tendency to form thesalt to any marked extent; and ifconducted at the lower range ofreaction temperatures, there. is a decided tendency to form theesterification products, rather than the amidification products.

Amide-type compounds can be converted into the ester type in the mannerdescribed in UrS. Patent No. 2,151,788, dated March 28, 1939, toMauersberger. Similarly, amides-in which there is an amino hydrogen atomattached to the amino nitrogen atom can be treated with an oxyalkylatingagent such as ethylene oxide, propylene oxide, glycidol, or the like, soas to introduce a hydroxy hydrocarbon radical. In the event that nohydroxy hydrocarbon radical is available for 'reaction with a materialsuch as nonaethylene glycol dihydrogen dimaleate, then in-that event,the acyl radical present must contain a hydroxyl radical. In otherWords, one must employ ricinoleic acid, hydroxystearic acid, or somesimilar equivalent.

In order to illustrate suitable examples of the hydroxylated amineswhich may be used as intermediate raw materials for reaction with thepolyalkylene glycol dihydrogendiacid ester, attention isdirected to thefollowing examples:

INTERMEDIATE HYDRoxYLA ED AMINE Example 1" Castor oil is employed. Forthe sake of con venience. its molecular weight is considered as being925. Commercial triethanolamine and castor oil in the proportion of onemole of castor oil and three moles of triethanolamine are heated to atemperature between 150180 C. for two hours. Mild agitation is employed.

The resultant obtained consists substantiall of the following compoundwhich has been.pre-.

' viously illustrated and in this specific instance that the ratioemployed is two moles of the castor oil to three'moles oftriethanolamine.

INTERMEDIATE HYDROXYLATED AMINE Example-'3 The same procedure isemployed as in .Intermediate hydroxylated amine, Example ,1, except thatthe ratio employed is three moles of castor oil to three moles oftriethanolamine.

. INTERMEDIATE HYDROXYLATED AMINE Example 4 One mole of methylnaphthenate is reacted in the manner previously described with onemoleculeof triethanolamine.

INTERMEDIATE HYDRoxYLATED AMINE Example 5 amples 1 and2, preceding, carebeing taken that INTERMEDIATE HYDROXYLATED AMINE.

Example 6 Methyl abietate is substituted for methyl naphthenate'inExamples l and 5, above.

INTERMEDIATE HYDROXYLATED AMINE I Example 7 I I Olive oil is substitutedfor castor oil in Ex.-

the'completed product contains droxyethyl group;

7 INTERMEDIllIEI-IYDROXYLATED AMI Example 8 at least one hy- Ethyldiethanolamine is substituted fortriethanolamine in Example 1,preceding.

INT RMEDIATE .HYDRoxYLATED AMINE Example 9 Jycloh exyl'diethanolamineis, substituted for .ethyl diethanolamine in theexample immediate lypreceding.

being 925; Commercialdiethanolamine and castor oil in the proportion pfone mole of castor oil to three moles. of diethano-lamine, are heated toa temperature l20-140 C. jfor about 12'hours. Mild agitation isemployed. Loss of bas'icity'is an indication of amidification. Time ofesterifica tion may be extended or temperature lowered or raised; so asto insure maximum esterification,

, and particularly, so as toproduce a product characteristics:

Acid number 13.2 to 25.0 Saponification number 230.5 to 274.0. Iodinenumber 43.5 to 55.0 Acetyl number; 164.0 to 192.0 Hydroxyl value 188.0to 220.0 Percent unsaponifiable matter 1.1 Percent nitrogen 0.0 PercentS03 0.0 Percent ash Trace acterized by the presence of one unesterifiedalkylol radical attached to the amino nitrogen.

INTERMEDIATE nwmxm A MIN Example 12 In the previousv examples ,wherecastoroil is employed, blown castor. oil is substituted there: for. Weprefer to use a drastically-oxidizedcastor oil having approximately thefollowing char-' .(See also UQS, Patent No. 2,225,824, dated December24, 1940, to De .Groote and Wirtel.)

The resultant obtained consists substantially of the following compoundwhich has been previously illustrated, and in-this specific instance,RCOO represents the acyloxy radical exemplifying the mixed blown castoroil acids which are Diethanolamine is substituted for triethanolamine inExample 4.

of unknown composition, although structurally,

' theymust-be somewhat akinito ricinoleic acid.

There is no single suitable formula available for depicting such acidsor their characteristic radicals:

'. RCOO.C2H4

H.C:HN

GLYCOL ESTER INTERMEDIATE PRODUCT Example 1 One pound mole ofnonaethylene glycol is reacted with two pound moles of maleic anhydride,so as to form nonaethylene glycol dihydrogen dimaleate. The reaction maybe shown more simply, as if involving the acid instead of the anhydride,thus:

The method of producing such fractional esters is well known. Thegeneral procedure is to employ a temperature above the boiling point, of

water and below the pyrolytic point of the reactants. The products aremixed and stirred constantly during the heating and esterification step.If desired, an inert gas, such as dried nitrogen, or dried carbondioxide, may be passed through the mixture. Sometimes it is desirable toadd an esterification catalyst, such as sulfuric acid, benzene sulfonicacid, or the like. This is the same general procedure as employed in themanufacture of ethylene glycol dihydrogen diphthalate. See U. S. PatentNo. 2,075,107, dated'March 30, 1937, to Frasier.

Sometimes esterification is conducted most readily in the presence of aninert solvent, that carries away the water of esterification which maybe formed, although, as is readily appreciated, such water ofesterification is absent when the reaction involves an acid anhydride,such as maleic anhydride, and a glycol. However, if water is formed, forinstance, when citric acid is employed, then a solvent such as xylenemay be u HOOC.C2H4COOEH HOECHflCHzOCHDsCH-zEOH H1OOC.C:H4.OOOH I ..Y

GLYCOL EsTER INTERMEDIATE PRODUCT Example 2 A mixture of lowernon-distillable polyethylene glycols, representing approximately decatotetradecaethylene glycol, is substituted for nonaethylene glycol in thepreceding example.

GLYcoL ESTER INTERMEDIATE PRODUCT Example 3 A 50-50 mixture ofnonaethylene glycol and lower non-distillable polyethylene glycols ofthe kind described in the previous example is substituted fornonaethylene glycol in Example 1.

GLYCOL EsTER INTERMEDIATE PRODUCT Example 4 Adipic acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

GLYCOL ESTER INTERMEDIATE PRODUCT Example 5 Oxalic acid is substitutedfor maleic anhydride in Examples 1-3, preceding;

GLYcoL ESTER INTERMEDIATE PRODUCT Example 6 Citric acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

GLYCDL ESTER INTERMEDIATE PRODUCT Example 7 Succinic anhydride issubstituted for maleic anhydride in Examples 1-3, preceding.

crntoocx gon n-cnnion Hi0 00.041.24.000 cmwmo omnomo o CLCzHnCO oin01mg?- iiii TIIII, e 01114.0 0 o a i on v E -931992 i m Hmcmoocmmcoomnolozm-u canon I -idom hydroxyl.

present and employed to carry off the water formed. The mixture ofxylene vapors and water vapors can be condensed so that the water isseparated. The xylene is then returned to the reaction vessel forfurther circulation. This is a conventional and well-known procedure andrequires no further elaboration.

COMPOSITION OF MATTER Example 1 Two pound moles of a tertiaryamine ofthe following composition:

Eooocui.

in which R.CO represents the ricinoleyl radical, are reacted with onepound mole of a glycol ester intermediate product of the kind describedunder Glycol ester intermediate products, Examples 1, 2 and 3,preceding. Such reaction is continued until substantially all carboxylacidity has disappeared. The time of reaction may vary from a few hoursto as many as 20 hours. It is to be noted that the reaction involvingnonaethylene dihydrogen dimaleate and the described ester, might involvethe acyl hydroxyl exclusively, or the alkylol hydroxyl exclusively, ormay involve both types. Thus, the resultant may be considered a mixtureof the following three, although one naturally assumes that the alkylolhydroxyl, being a primary hydroxyl, would-react in preference to theacyl hydroxyl, which is a secondary The ricinoleyl radical RCO containsa hydroxyl group, and thus, for convenience, may be rewritten HO.R."'CO.

COMPOSITION or Marn i Example 2 I i A comparable compound of the kindpreviously described is obtained from tripropanolamine' instead oftriethanolamine.

I COMPOSITION or MATTER Eiample 3 Materials of the kind described inComposition ,ofmatter, Examples 1 and' 2, are obtained from 's'oyabeanfatty acids instead of castor oil fatty COMPOSITION or MA'r'rEn Example4 Glycol esterintermediate products of the kind exemplified by Examples4-7, preceding, are sub stituted for Glycol intermediate products,Examlples l, 2, and 3 in the precedin three'examples.

. It is to be noted that this second step isan esterificationreaction,1,and the same procedure is employed, assuggested above, in thepreparation of the intermediate product. Needlessito say, any particularmethod-may be used to produce thefl'desiredcompounds of the kindindiecated. In some'inst'ancesit may be desirable'to conduct theesterification reaction in the presence of a non-volatile inert solventWhichsimply actsasadiluent or viscosityreducer; q 3 In-the precedingexamples, attention has been directed primarily to themonomeric form, orat least, to the form in which the bifunctional alcohol, i. ve., aglycol; and the. polyfunctional acid,

usually a bifunctional compound, react to give a chain'type compound, inwhich the adjacentacid 'anhydride and two moles of nonaethylene glycol,

the tendency would be to produce a product which might be indicated inthe following manner:

.acid glycol =lcid1. glycol .ncid

Similarly, three moles of theglycol nd fpur moles of the acid might tendto give a combi-f nation which may beindicated thus:

acid glycol acid glycol acid glycol .acid

Another'way of stating the matter is that the composition may bindicated in the following manner: 7 I

TOj OC .D.CO'O (CzHr'O) mlC2H4OOC.D.COO]rT in which the characters havetheir previous significance and-a: is a relatively small whole numberless than 10 andprobably' less than 5; and in the monomeric form :r, ofcourse,'is 1. The limitations on the size of :r are probably influ--enced largely by=the fact that reaction leading to further growthcontact. l

Someof the products are self-emulsifiable oils or self-emulsifiablecompounds; whereas, others give cloudy solutions or sols; and the mostdesirable type is characterized by giving a clear solution in water, andusually in the presence of soluble calcium or magnesium salts, andfrequently, in the presence of significant-amounts of either acids oralkalies. r I z.

Water solubility can be enhanced in a number is dependent 'upon' randomace-1329 of ways-which have beenysugge'sted by previous manufacturingdirections, for instance (6) By 'using'a more highly polymerized ethylene glycol;

(b) Byusing a polymeric form instead of a monomeri'ciorm in regard to"the unit which forms the chainbetween the two alcoholic nuclei; (0);"By using a polybasic carboxy acid "of lower molecular weight, forinstance, maleic acid,'i'nst a er adipic acid; 1 1 r )iBy usinga'n'amine of a lower molecular were ei-"having more'hydroxyl groups, as,for'eiramplel'a derivative of glycerylamine. Indeed, "in many'instances,the hydroxylat'ed 'acylated'amino compound is water-solubleprior toreactionwith a glycol ester. It is to be noted that-in'this instance,one is notlimitedto hydro'x'ylated materials "which are water-insolubleprior tofreaction with a glycol ester; but may, in fact, beperfectlywater-soluble.

Actually, a reaction involving analcohol and an; acid (e'sterification)amounts'of either one or both of' thef'reactants', depending upon thepredetermined proportion, tovremain in an unreacted' state. In theactual preparationof compositions of the kind'herein contemplated, anyresidual acidity can be rej+ moved by any suitable 'base," ror instance,am-

' th y monia, triethanolamine, orthe like, especially in dilutesolution. Naturally, precaution should be taken,'so that neutralizationtakes place without sap'onif cation or decomposition of the ester. Insome" cases there isno objection to the presence of'the acidic group;Indeed, if 'ajtribasic acid be employed in such almanner astoleaveone-'free' carboxyl group, then it is usually de; 'sirable to neutralizesuch group b 'means of a "s'uitable'basic'material. j 3 j Infthe heretoappended claims, reference'to a neutral productrefers to one in which;free'carboxylic radicals are absent,

Materials of the kind herein contemplated may find uses as wetting.detergent, and leveling ,agents in the laundry, textile, and dyeingind'ustry; ,as Wetting agentsand. detergents in the acid washing offruit, in. the acid washingof.

building stone and brick; as a wetting agent and spreader in theapplication of asphalt in road building and the like, as a constituentof soldering flux preparations; as a fiotationreagent in l the flotationseparation of various minerals; for

1 and various trade wastes and the like; as germicides, insecticides,emulsifiers for cosmetics, spray oils, water-repellant textile finish,etc. These uses are by no meansexhaustive.

However, the most important phase of the present invention, as far asindustrial application goes, i s concerned with the use of the materialspreviously. described asdemulsifiers for water-in, oil emulsions, andmore specifically, emulsions of wateror brine in crude petroleum.'flfsflnlwljlat analogous use of our'demulsi fying agent iSthe removalof a residual mud sheath which remains afterdrilling by the rotarymethod Sometimes the drilling mud contains added calcium carbonate or.the like .to render the mud susceptible togreaction with hydrochloricacid or the like, and thus expedite its removal.

Chemical compounds of the kind herein described are also of valueassurface tensionde' pressantsziin the. acidization ofcalcareous "oil'-bearing strata by"=means of strong mineral acid,

may permit :smal l bearing strata. As to using compounds of the kindherein described as flooding agents for recovering oil from subterraneanstrata, reference is made to the procedure described in detail in U. S.PatentNo. 2,226,119, dated December 24, 1940, to De Groote and Keiser.As to using compounds of the kind herein described as demulsifiers, orin particular as surface tension depressants, in combination withmineral acid or acidization of oil-bearing strata, reference is made toU. S. Patent No. 2,233,383, dated February 25, 1941, to De Groote andKeiser.

It will be apparent to those skilled in the art that residual carboxylacidity can be eliminated by esterification with a low molal alcohol,for instance, ethyl, methyl, or propyl alcohol, by conventionalprocedure, so as to give a substantially neutral product. Theintroduction of such low molal hydrophobe groups does not seriouslyaffect the solubility, and in some instances, gives increasedresistance, to soluble calcium and magnesium salts, for such property isof particular value. Usually, however, neutralization with a dilutesolution of ammonia or the like is just as practicable and lessexpensive.

In the hereto appended claims, it is intended that the monomeric formscontemplate also the polymeric forms, insofar that the polymeric formsare nothing more or less than a repetition of the monomeric formsseveral times over, with the loss of one or more moles of water.

What has just been said can be recapitulated and presented in moreformal agreement with customary nomenclature in the following manner: Asstated previously in the broadest aspect, the polyalkylene glycolsemployed may be indicated by the following formula:

omctnaolmn in which m has its previous significance, and n represents anumeral varying from 2 to 4. In simpler form, this structur can beindicated in .the following manner:

in which the divalent radical --RO- is the divalent radical--(CnH2nO)mas previously defined.

The dibasic acid previously referred to, in its simplest form asHOOC.D.C'OOH, is more completely portrayed by the following formula:

COOH

Rr-COOH (Co OH) in which R1 is the polybasic carboxy acid residue,except in the unique case of oxalic acid, and n is the numeral or 1,depending on whether or not the polybasic acid is dibasic or tribasic.

If the polybasic acid just described is indicated by R, and if theglycol just described is indicated by R", then the acidic 0r fractionalester previously described in the specification may be indicated by thefollowing formula:

V [o]. M, at]

in which p and p represent numerals varying from 1 to 10, and representsa numeral varying from 1 to 20, and R and B" have their priorsignificance, and the ratio of p to p varies from 2:1 to p+1:p', withthe obvious proviso that such ester must contain at least two freecarboxyl radicals. i

Previous reference has been made to the hydroxylated acylatedaminoalcohol free from ether linkages and of the following composition:

ntooocflnmm' Nmnm ouonrrmm' in which R4900 represents the oxyacylradical derived from a monocarboxy detergent-forming acid having atleast 8 and not more than 32 carbon atoms; R2 represents a member of theclass consisting of hydrogen atoms, non-hydroxyl hydrocarbon radicals,and acylated radicals, obtained by replacing a, hydrogen atom of thehydroxyl group of an alkylol radical by the acyl radical of a monobasiccarboxy acid having less than eight carbon atoms; n represents a smallwhole number which is less than 10; m represents the numeral 1, 2, or 3;m" represents the numeral 0, 1, or 2; and m'" represents the numeral 0,1, or 2, with the proviso that m'+m"+m"'=3. v

' It is more convenient to consider the previous compound as an alcoholof the formula:

in which m"" varies from 1 to 3, R3 is the radical obtained by thedehydroxylation of the previously described hydroxylated acylated'aminoalcohol. It is to be noted that one or more of the hydroxyls maybe part of an acyl radical, such as a ricinoleyl radical, or part of analkylol radical, such as an ethanol radical.

The composition of matter herein contemplated is best represented as anester obtained by the esterification reaction involving the acidicfractional ester above described, and the hydroxylated acylatedaminoalcohol previously depicted in detail. The final composition may beobtained in any suitable manner and would properly represent the finalproduct, regardless of the succession of intermediate steps. Soportrayed, the structural formula is as follows:

in which n" represents a numeral varying from 1 to 3, n represents anumeral varying from 1 to 4, and n'' represents a numeral varying from 1to 4.

It has been previously pointed out in the specification that anyresidual carboxylio radicals, and especially one obtained from tribasicacids, could be neutralized with a variety of suitable basic materials.In other words, a residual carboxylic hydrogen atom may be replaced by ametallic atom, an ammonium radical, or substituted ammonium radical, aspreviously indicated. Under such circumstances, any residual carboxylioradical, instead of appearing thus: COOH, may, in essence, be theradical COOR4 in which R4 represents a cation including the acidichydrogen atom. This can be best disposed of by rewriting the formula forthe polybasic carboxy acid, thus:

- coon Ri COOH COOROM in which all of the characters have theirpriorsignificance.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A water-soluble ester of the formula:

I llll in which n" represents a numeral varying from 1 to 3, and n'represents a numeral varying from 1 to 4, and n"" represents a numeralvarying from 1 to 4, and in which p and p represent (COOROM in which R1is the polycanboxy acid residue, and

R4 is a cation, and n is the numeral or 1,

R3(OH)m"" is a hydroxylated acylated aminoalcohol in which m""represents a numeral from 1 to 3, and R3 is the dehydroxylated residueof the hydroxylated acylated aminoalcohol of the formula:

RrcoooflHmm' in which R4.C00 represents the oxyacyl radical derived froma monocarboxy detergent-forming acid having at least 8 and not more than32 carbon atoms; R2 represents a member of the class consisting ofhydrogen atoms, non-hydroxyl hydrocarbon radicals, and acylated radicalsobtained by replacing a hydrogen atom of the hydroxyl group of analkylol radical by the acyl radical of a monobasic carboxy acid havingless than 8 carbon atoms; n represents a small whole number which isless than n represents the numeral 1, 2, or 3; 122" represents thenumeral 0, 1, or 2; and m' represents the numeral 0, l, or 2, with theproviso that m'+m+m'=3.

2. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0.

3. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, and n represents the numeral 2.

4. A water-soluble ester, as defined in claim 1, wherein all occurrencesof nare 0, n represents the numeral 2, and m represents a numeralvarying from '7 to 11.

5. A water-soluble ester, as defined in claim 1,

.- wherein all occurrences of n are 0, n represents the numeral 2, mrepresents a numeral varying from 7 to 11, and R400 is an 18 carbon atomfatty acid residue.

6. A water-soluble ester, as defined in claim 1,

wherein all occurrences of n are 0, n represents the numeral 2, mrepresents a numeral varying from 7 to 11, R400 is an 18 carbon atomfatty acid residue, and the ratio of p to p is 2 to 1.

7. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, 117. represents a numeral varyinfrom 7 to 11, R4CO is an 18 carbon atom fatty acid residue, the ratio ofp to p is 2 to 1, and with added neutralization of-all residual acidity.

8. A Water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, m represent a numeral varyingfrom 7 to 11, R400 is a ricinoleic acid residue, the ratio of p to p is2 to l, and. with added neutralization of all residual acidity.

9. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, m represents a numeral varyingfrom 7 to 11, R400 i a ricinoleic acid residue, the ratio of p to p is 2to 1, with added neutralization of all residual acidity, and R1 is anadipic acid residue.

10. A water-soluble ester, as defined in claim 1, wherein alloccurrences of n are 0, n represents the numeral 2, m represents anumeral varying from 7 to 11, R400 is a ricinoleic acid residue, theratio of p to p. is 2. to 1, with added neutralization of all residualacidity, and R1 is a succinic acid residue. 1

11. A Water-soluble ester, as defined in claim 1, wherein alloccurrences of n are 0, n represents the numeral 2, m represents anumeral varying from 7 to 11, R400 is a ricinoleic acid residue, theratio of p to p is 2 to 1, with added neutralization of all residualacidity, and R1 is a maleic acid residue.

12. In the manufacture of the esterification product of the kinddescribed in claim 1, the steps of: (A) esterifying a polyalkyleneglycol having at least 7 and not more than 17 ether linkages; and thealkylene radical thereof containing at I least 2 and not more than 6carbon atoms; with (0H. cum) m in which H.000 represents the oxyacylradical derived from a monobasic detergent-forming acid; obtained byreplacing a hydrogen atom of the hydroxyl group of an alkylol radical bythe acyl radical of a monobasic carboxy acid having less than 8 carbonatoms; n represents a small whole number which is less than 10; mrepresents the numeral 1, 2, or 3; 111/ represents the numeral 0, 1, or2'; and m" represents the numeral 0, 1, or 2, with the proviso thatMELVIN DE GROOTE. BERNHARD KEISER.

